Stannoxy-substituted metallocene catalysts for olefin and acetylene polymerization

ABSTRACT

This invention relates to the field of olefin polymerization catalyst compositions, and methods for the polymerization and copolymerization of olefins, including polymerization methods using a catalyst composition. One aspect of this invention is the formation and use of a catalyst composition comprising a stannoxy-substituted half-sandwich metallocene and an activator for olefin polymerization processes. For example, this invention encompasses the preparation of (η 5 -C 5 H 5 )Ti(OSnPh 3 )Cl 2 , its contact with an activator, for example, zinc-impregnated chlorided alumina, to form a catalyst composition, and the use of this catalyst composition for polymerizing olefins or acetylenes.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of organometal compositions, olefinpolymerization catalyst compositions, methods for the polymerization andcopolymerization of olefins using a catalyst composition, andpolyolefins.

BACKGROUND OF THE INVENTION

It is known that olefins, including ethylene, can be polymerized withcatalyst compositions employing titanium, zirconium, vanadium, chromiumor other metals, impregnated on a variety of support materials, often inthe presence of cocatalysts. These catalyst compositions may be usefulfor both homopolymerization of ethylene, as well as copolymerization ofethylene with comonomers such as propylene, 1-butene, 1-hexene, or otherhigher α-olefins. Therefore, there exists a constant search to developnew olefin polymerization catalysts, catalyst activation processes, andmethods of making and using catalysts, that will provide enhancedcatalytic activities and polymeric materials tailored to specific enduses.

One type of catalyst system comprises organometal compounds,particularly metallocene compounds. A special class of metallocenes thathas been little explored are the half-sandwich metallocenes, whichcontain only a single η⁵-cyclopentadienyl-type ring system. It isbelieved that such compounds may offer the potential for higher activityand better comonomer incorporation. Also of interest is the developmentof metallocene-based catalytic systems that can be activated with avariety of activating agents without requiring relatively expensivemethylaluminoxane, yet still provide relatively high polymerizationactivities.

Therefore, what are needed are new catalyst compositions and methods ofmaking the catalyst compositions that afford high polymerizationactivities, and will allow polymer properties to be maintained withinthe desired specification ranges.

SUMMARY OF THE INVENTION

This invention comprises catalyst compositions, methods for preparingcatalyst compositions, and methods for polymerizing olefins andacetylenes using the catalyst compositions disclosed herein. In thecourse of examining metallocene olefin polymerization catalysts, thepreparation and properties of new half-sandwich metallocene compoundswere investigated. It was discovered that half-sandwich metallocenecompounds can be contacted with an activator to form a catalystcomposition for the polymerization of olefins and acetylenes. Thepresent invention encompasses new compounds, new compositions of matter,and new catalyst compositions comprising half-sandwich metallocenecompounds of the following general formula:(X¹)(X²)(X³)(X⁴)M¹; wherein

-   -   M¹ is selected from titanium, zirconium, or hafnium;    -   (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,        substituted cyclopentadienyl, substituted indenyl, or        substituted fluorenyl;    -   each substituent on the substituted cyclopentadienyl,        substituted indenyl, or substituted fluorenyl (X¹) is        independently selected from an aliphatic group, an aromatic        group, a cyclic group, a combination of aliphatic and cyclic        groups, an oxygen group, a sulfur group, a nitrogen group, a        phosphorus group, an arsenic group, a carbon group, a silicon        group, a germanium group, a tin group, a lead group, a boron        group, an aluminum group, an inorganic group, an organometallic        group, or a substituted derivative thereof, any one of which        having from 1 to about 20 carbon atoms; a halide; or hydrogen;    -   (X²) is selected from a stannoxy group with the following        formula:        —OSnR₃;    -   wherein R is independently selected from alkyl, cycloalkyl,        aryl, aralkyl, substituted alkyl, substituted aryl, or        substituted aralkyl, any one of which having from 1 to about 20        carbon atoms; OR′ wherein R′ is selected from alkyl, aryl,        aralkyl, substituted alkyl, substituted aryl, or substituted        aralkyl, any one of which having from 1 to about 20 carbon        atoms; F; Cl; Br; or I; and    -   (X³) and (X⁴) are independently selected from an aliphatic        group, an aromatic group, a cyclic group, a combination of        aliphatic and cyclic groups, an oxygen group, a sulfur group, a        nitrogen group, a phosphorus group, an arsenic group, a carbon        group, a silicon group, a germanium group, a tin group, a lead        group, a boron group, an aluminum group, an inorganic group, an        organometallic group, or a substituted derivative thereof, any        one of which having from 1 to about 20 carbon atoms; or a        halide.

In one aspect, the catalyst composition of this invention comprises anactivator. Several different activators may be used to activate thehalf-sandwich metallocenes of this invention including, but not limitedto, an aluminoxane, an organoboron compound, an ionizing ionic compound,an ion-exchangeable layered compound exchanged with anelectron-withdrawing anion, a chemically-treated solid oxide combinedwith an organoaluminum compound, or a mixture of any or all of theseactivator components.

In another aspect of this invention, the activator comprises achemically-treated solid oxide, which comprises a solid oxide treatedwith an electron-withdrawing anion. In yet another aspect of thisinvention, the activator comprises a chemically-treated solid oxide incombination with an organoaluminum compound.

In still another aspect, the catalyst composition of this inventioncomprises:

-   -   a) a half-sandwich metallocene compound;    -   b) a chemically-treated solid oxide comprising a solid oxide        treated with an electron-withdrawing anion, wherein    -   the solid oxide is selected from silica, alumina,        silica-alumina, aluminum phosphate, heteropolytungstates,        titania, zirconia, magnesia, boria, zinc oxide, mixed oxides        thereof, or mixtures thereof; and    -   the electron-withdrawing anion is selected from fluoride,        chloride, bromide, phosphate, triflate, bisulfate, sulfate, or        combinations thereof; and    -   c) an organoaluminum compound with the following formula:        Al(X⁵)_(n)(X⁶)_(3-n);        wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon        atoms; (X⁶) is selected from alkoxide or aryloxide, any one of        which having from 1 to about 20 carbon atoms, halide, or        hydride; and n is a number from 1 to 3, inclusive.

In another aspect of this invention, for example, the half-sandwichmetallocene compound CpTi(OSnPh₃)Cl₂, where Cp=η⁵-C₅H₅, is prepared andis employed along with triisobutylaluminum cocatalyst and achemically-treated solid oxide comprising fluorided silica-alumina,sulfated alumina, or chlorided alumina. Further, the chemically-treatedsolid oxide optionally contains another metal or metal ion, includingbut not limited to, zinc. As used herein the chemically-treated solidoxide is also termed an “activator-support”, of which fluoridedsilica-alumina, sulfated, and chlorided alumina are examples. Notwishing to be bound by theory, it is believed that the acidicactivator-support is not merely an inert support component of thecatalyst composition, but is involved in effecting the observedcatalytic chemistry.

This invention also encompasses methods of making catalyst compositionsthat comprise contacting at least one half-sandwich metallocene compoundand an activator, including but not limited to, an organoaluminumcompound combined with a chemically-treated solid oxide. These methodsalso comprise contacting the half-sandwich metallocene catalyst, theorganoaluminum cocatalyst, and the chemically-treated solid oxide, andoptionally pretreating some or all of these components with an olefin oracetylene compound, prior to initiating the polymerization reaction.

The present invention further comprises methods for polymerizing olefinscomprising contacting at least one olefin monomer and a catalystcomposition under polymerization conditions to produce the polymer.

Another aspect of this invention is the polyolefins described herein.

This invention also encompasses an article that comprises the polymerproduced with the catalyst composition of this invention.

These and other features, aspects, embodiments, and advantages of thepresent invention will become apparent after a review of the followingdetailed description of the disclosed features.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the ¹H NMR spectrum of the half-sandwich metallocenecompound (η⁵-C₅H₅)Ti(OSnPh₃)Cl₂, recorded in CDCl₃ solvent at 300 MHz.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new catalyst compositions, methods forpreparing catalyst compositions, and methods for using the catalystcompositions to polymerize olefins and acetylenes. In accordance withthis invention, the catalyst composition comprises at least onehalf-sandwich metallocene compound and an activator. The activator ofthis invention is typically selected from an aluminoxane, an organoboroncompound, an ionizing ionic compound, a clay material, achemically-treated solid oxide combined with an organoaluminum compound,or any combination thereof.

In accordance with this invention, when the activator is a combinationor mixture of a chemically-treated solid oxide and an organoaluminumcompound, the solid oxide has been treated with an electron-withdrawinganion from an ionic or molecular species, or from a source compound ofany type, and optionally treated with another metal in addition to anelectron-withdrawing anion.

Catalyst Composition—The Half-Sandwich Metallocene

The present invention provides new compounds, new compositions ofmatter, new catalyst compositions comprising half-sandwich metallocenecompounds, new methods for preparing catalyst compositions and newmethods for polymerizing olefins. In one aspect, this invention providescatalyst compositions comprising one or more half-sandwich metallocenesand an activator component. In one aspect, the half-sandwich metalloceneof this invention comprises a metal selected from titanium, zirconium,or hafnium. In another aspect, the half-sandwich metallocene may be astannoxy-substituted metallocene compound having the following generalformula:(X¹)(X²)(X³)(X⁴)M¹; wherein

-   -   M¹ is selected from titanium, zirconium, or hafnium;    -   (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,        substituted cyclopentadienyl, substituted indenyl, or        substituted fluorenyl;    -   each substituent on the substituted cyclopentadienyl,        substituted indenyl, or substituted fluorenyl (X¹) is        independently selected from an aliphatic group, an aromatic        group, a cyclic group, a combination of aliphatic and cyclic        groups, an oxygen group, a sulfur group, a nitrogen group, a        phosphorus group, an arsenic group, a carbon group, a silicon        group, a germanium group, a tin group, a lead group, a boron        group, an aluminum group, an inorganic group, an organometallic        group, or a substituted derivative thereof, any one of which        having from 1 to about 20 carbon atoms; a halide; or hydrogen;    -   (X²) is selected from a stannoxy group with the following        formula:        —OSnR₃;    -   wherein R is independently selected from alkyl, cycloalkyl,        aryl, aralkyl, substituted alkyl, substituted aryl, or        substituted aralkyl, any one of which having from 1 to about 20        carbon atoms; OR′ wherein R′ is selected from alkyl, aryl,        aralkyl, substituted alkyl, substituted aryl, or substituted        aralkyl, any one of which having from 1 to about 20 carbon        atoms; F; Cl; Br; or I; and    -   (X³) and (X⁴) are independently selected from an aliphatic        group, an aromatic group, a cyclic group, a combination of        aliphatic and cyclic groups, an oxygen group, a sulfur group, a        nitrogen group, a phosphorus group, an arsenic group, a carbon        group, a silicon group, a germanium group, a tin group, a lead        group, a boron group, an aluminum group, an inorganic group, an        organometallic group, or a substituted derivative thereof, any        one of which having from 1 to about 20 carbon atoms; or a        halide.

Substituents on the substituted cyclopentadienyls, substituted indenyls,and substituted fluorenyls of (X¹), the (X³) ligand, and the (X⁴) ligandare independently selected and include, but are not limited to, analiphatic group, an aromatic group, a cyclic group, a combination ofaliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogengroup, a phosphorus group, an arsenic group, a carbon group, a silicongroup, a germanium group, a tin group, a lead group, a boron group, analuminum group, an inorganic group, an organometallic group, or asubstituted derivative thereof, any one of which having from 1 to about20 carbon atoms; a halide; or hydrogen; as long as these groups do notterminate the activity of the catalyst composition. Thus, the terms“substituted indenyls” and “substituted fluorenyls” are also used hereinto include partially saturated indenyls and fluorenyls including, butnot limited to, tetrahydroindenyls, terahydro-fluorenyls, andoctahydrofluorenyls.

For the formula (X¹)(X²)(X³)(X⁴)M¹, examples of chemical moieties orgroups that may be selected as substituents on the substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls of(X¹), include, but are not limited to, the following groups. Unlessotherwise specified, R is independently selected from: an aliphaticgroup; an aromatic group; a cyclic group; any combination thereof; anysubstituted derivative thereof, including but not limited to, a halide-,an alkoxide-, or an amide-substituted derivative thereof; any one ofwhich has from 1 to about 20 carbon atoms; or hydrogen.

Examples of aliphatic groups, in each instance, include, but are notlimited to, an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclicgroup, and the like, and includes all substituted, unsubstituted,branched, and linear analogs or derivatives thereof, in each instancehaving from one to about 20 carbon atoms. Thus, aliphatic groupsinclude, but are not limited to, hydrocarbyls such as paraffins andalkenyls. For example, aliphatic groups as used herein include methyl,ethyl, propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, amyl, isoamyl,hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl,pentenyl, butenyl, and the like.

Examples of cyclic groups, in each instance, include, but are notlimited to, cycloparaffins, cycloolefins, cycloacetylenes, arenes suchas phenyl, bicyclic groups and the like, including substitutedderivatives thereof, in each instance having from about 3 to about 20carbon atoms. Thus heteroatom-substiuted cyclic groups such as epoxylare included herein.

Examples of halides, in each instance, include fluoride, chloride,bromide, and iodide.

In each instance, oxygen groups are oxygen-containing groups, examplesof which include, but are not limited to, alkoxy or aryloxy groups(—OR), —OC(O)R, —OC(O)H, —OSiR₃, —OPR₂, —OAlR₂, and the like, includingsubstituted derivatives thereof, wherein R in each instance is selectedfrom alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substitutedaryl, or substituted aralkyl having from 1 to about 20 carbon atoms.Examples of alkoxy or aryloxy groups (—OR) groups include, but are notlimited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substitutedphenoxy, and the like.

In each instance, sulfur groups are sulfur-containing groups, examplesof which include, but are not limited to, —SR, —OSO₂R, —OSO₂OR, —SCN,—SO₂R, and the like, including substituted derivatives thereof, whereinR in each instance is selected from alkyl, cycloalkyl, aryl, aralkyl,substituted alkyl, substituted aryl, or substituted aralkyl having from1 to about 20 carbon atoms.

In each instance, nitrogen groups are nitrogen-containing groups, whichinclude, but are not limited to, —NH₂, —NHR, —NR₂, —NO₂, —N₃, and thelike, including substituted derivatives thereof, wherein R in eachinstance is selected from alkyl, cycloalkyl, aryl, aralkyl, substitutedalkyl, substituted aryl, or substituted aralkyl having from 1 to about20 carbon atoms.

In each instance, phosphorus groups are phosphorus-containing groups,which include, but are not limited to, —PH₂, —PHR, —PR₂, —P(O)R₂,—P(OR)₂, —P(O)(OR)₂, and the like, including substituted derivativesthereof, wherein R in each instance is selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl having from 1 to about 20 carbon atoms.

In each instance, arsenic groups are arsenic-containing groups, whichinclude, but are not limited to, —AsHR, —AsR₂, —As(O)R₂, —As(OR)₂,—As(O)(OR)₂, and the like, including substituted derivatives thereof,wherein R in each instance is selected from alkyl, cycloalkyl, aryl,aralkyl, substituted alkyl, substituted aryl, or substituted aralkylhaving from 1 to about 20 carbon atoms.

In each instance, carbon groups are carbon-containing groups, whichinclude, but are not limited to, alkyl halide groups that comprisehalide-substituted alkyl groups with 1 to about 20 carbon atoms, aralkylgroups with 1 to about 20 carbon atoms, —C(O)H, —C(O)R, —C(O)OR, cyano,—C(NR)H, —C(NR)R, —C(NR)OR, and the like, including substitutedderivatives thereof, wherein R in each instance is selected from alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each instance, silicon groups are silicon-containing groups, whichinclude, but are not limited to, silyl groups such alkylsilyl groups,arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like,which in each instance have from 1 to about 20 carbon atoms. Forexample, silicon groups include trimethylsilyl and phenyloctylsilylgroups.

In each instance, germanium groups are germanium-containing groups,which include, but are not limited to, germyl groups such alkylgermylgroups, arylgermyl groups, arylalkylgermyl groups, germyloxy groups, andthe like, which in each instance have from 1 to about 20 carbon atoms.

In each instance, tin groups are tin-containing groups, which include,but are not limited to, stannyl groups such alkylstannyl groups,arylstannyl groups, arylalkylstannyl groups, stannoxy (or “stannyloxy”)groups, and the like, which in each instance have from 1 to about 20carbon atoms. Thus, tin groups include, but are not limited to, stannoxygroups.

In each instance, lead groups are lead-containing groups, which include,but are not limited to, alkyllead groups, aryllead groups, arylalkylleadgroups, and the like, which in each instance, have from 1 to about 20carbon atoms.

In each instance, boron groups are boron-containing groups, whichinclude, but are not limited to, —BR₂, —BX₂, —BRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each instance is selected from alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

In each instance, aluminum groups are aluminum-containing groups, whichinclude, but are not limited to, —AlR₂, —AlX₂, —AlRX, wherein X is amonoanionic group such as halide, hydride, alkoxide, alkyl thiolate, andthe like, and wherein R in each instance is selected from alkyl,cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, orsubstituted aralkyl having from 1 to about 20 carbon atoms.

Examples of inorganic groups that may be used as substituents forsubstituted cyclopentadienyls, substituted indenyls, substitutedfluorenyls, and substituted boratabenzenes, in each instance, include,but are not limited to, —SO₂X, —OAlX₂, —OSiX₃, —OPX₂, —SX, —OSO₂X,—AsX₂, —As(O)X₂, —PX₂, and the like, wherein X is a monoanionic groupsuch as halide, hydride, amide, alkoxide, alkyl thiolate, and the like,and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl group or substituent on theseligands has from 1 to about 20 carbon atoms.

Examples of organometallic groups that may be used as substituents forsubstituted cyclopentadienyls, substituted indenyls, and substitutedfluorenyls, in each instance, include, but are not limited to,organoboron groups, organoaluminum groups, organogallium groups,organosilicon groups, organogermanium groups, organotin groups,organolead groups, organo-transition metal groups, and the like, havingfrom 1 to about 20 carbon atoms.

In one aspect of this invention, (X³) and (X⁴) are independentlyselected, and include, but are not limited to, the following groups andtheir substituted derivatives: halides, alkoxides having from 1 to about10 carbon atoms, or hydrocarbyls having from 1 to about 10 carbon atoms.In another aspect of this invention, (X³) and (X⁴) are selected fromchloro, bromo, methyl, benzyl, or trifluoromethylsulfonyl. In yetanother aspect, (X³) and (X⁴) are chloro.

In still another aspect of this invention, the half-sandwich metallocenecompound used in this invention has the following general formula:(η⁵-cycloalkadienyl)M(OSnR₃)X₂; wherein

-   -   cycloalkadienyl is selected from cyclopentadienyl, indenyl,        fluorenyl, or substituted analogs thereof;    -   M is selected from Ti, Zr, or Hf;    -   R is independently selected from substituted or non-substituted        alkyl, cycloalkyl, aryl, aralkyl, alkoxide, or aryloxide, any        one of which having from 1 to about 20 carbon atoms; F; Cl; Br;        or I; and    -   X is independently selected from F; Cl; Br; I; or a substituted        or non-substituted alkyl, cycloalkyl, aryl, aralkyl, alkoxide,        or aryloxide, any one of which having from 1 to about 20 carbon        atoms.

Numerous processes to prepare metallocenes that can be employed in thisinvention have been reported. For example, U.S. Pat. Nos. 4,939,217,5,210,352, 5,436,305, 5,401,817, 5,631,335, 5,571,880, 5,191,132,5,480,848, 5,399,636, 5,565,592, 5,347,026, 5,594,078, 5,498,581,5,496,781, 5,563,284, 5,554,795, 5,420,320, 5,451,649, 5,541,272,5,705,478, 5,631,203, 5,654,454, 5,705,579, and 5,668,230 describe suchmethods, each of which is incorporated herein by reference, in itsentirety. The following treatises also describe such methods: Wailes, P.C.; Coutts, R. S. P.; Weigold, H. in Organometallic Chemistry ofTitanium, Zironium, and Hafnium, Academic; New York, 1974.; Cardin, D.J.; Lappert, M. F.; and Raston, C. L.; Chemistry of Organo-Zirconium and-Hafnium Compounds; Halstead Press; New York, 1986.

As used herein, half-sandwich metallocene compound includesmonokis(cyclopentadienyl) compounds, monokis(indenyl) compounds,monokis(fluorenyl) compounds, and their substituted analogs. Examples ofsuch half-sandwich, stannoxy-substituted metallocene compounds that areuseful in the present invention include, but are not limited to, thefollowing compounds:

and the like.

In one aspect of this invention, the half-sandwich metallocene compoundis selected from(η⁵-cyclopentadienyl)titanium(triphenylstannoxy)dichloride or(η⁵-cyclopentadienyl)zirconium(triphenylstannoxy)dichloride.

Catalyst Composition—The Activator

In addition to the half-sandwich metallocenes disclosed herein, thecatalyst composition of this invention further comprises an activator.In one aspect of this invention, the activator is selected from analuminoxane, an organoboron compound, an ionizing ionic compound, a claymaterial, a chemically-treated solid oxide combined with anorganoaluminum compound, or any combination thereof. In another aspectof the invention, the clay material is selected from clays and othernatural and synthetic layered oxides, cogelled clay matrices containingsilica or other oxides, pillared clays, zeolites, clay minerals, otherlayered minerals, or combinations thereof, including, but not limitedto, ion-exchangeable layered minerals (natural or synthetic) orcomposites made from such compounds, regardless of whether the layeredstructure remains intact or not. The activator may further comprise acombination or mixture of any of these activators.

The Chemically-Treated Solid Oxide

In one aspect, the present invention encompasses catalyst compositionscomprising a chemically-treated solid oxide which serves as an acidicactivator-support, and which is typically used in combination with anorganoaluminum compound. In one aspect, the chemically-treated solidoxide comprises a solid oxide treated with an electron-withdrawinganion; wherein the solid oxide is selected from silica, alumina,silica-alumina, aluminum phosphate, heteropolytungstates, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixturesthereof; and wherein the electron-withdrawing anion is selected fromfluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, orany combination thereof.

The chemically-treated solid oxide includes the contact product of atleast one solid oxide compound and at least one electron-withdrawinganion source. In one aspect, the solid oxide compound comprises aninorganic oxide. It is not required that the solid oxide compound becalcined prior to contacting the electron-withdrawing anion source. Thecontact product may be calcined either during or after the solid oxidecompound is contacted with the electron-withdrawing anion source. Inthis aspect, the solid oxide compound may be calcined or uncalcined. Inanother aspect, the chemically-treated solid oxide may comprise thecontact product of at least one calcined solid oxide compound and atleast one electron-withdrawing anion source.

The chemically-treated solid oxide exhibits enhanced acidity as comparedto the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also functions as a catalyst activator ascompared to the corresponding untreated solid oxide. While not intendingto be bound by theory, it is believed that the chemically-treated solidoxide may function as an ionizing solid oxide compound by completely orpartially extracting an anionic ligand from the metallocene. However,the chemically-treated solid oxide is an activator regardless of whetherit is ionizes the metallocene, abstracts an anionic ligand to form anion pair, weakens the metal-ligand bond in the metallocene, simplycoordinates to an anionic ligand when it contacts the chemically-treatedsolid oxide, or any other mechanisms by which activation may occur.While the chemically-treated solid oxide activates the metallocene inthe absence of cocatalysts, it is not necessary to eliminate cocatalystsfrom the catalyst composition. The activation function of thechemically-treated solid oxide is evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositioncontaining the corresponding untreated solid oxide. However, it isbelieved that the chemically-treated solid oxide functions as anactivator, even in the absence of organoaluminum compound, aluminoxanes,organoboron compounds, or ionizing ionic compounds.

In one aspect, the chemically-treated solid oxide of this inventioncomprises a solid inorganic oxide material, a mixed oxide material, or acombination of inorganic oxide materials, that is chemically-treatedwith an electron-withdrawing component, and optionally treated with ametal. Thus, the solid oxide of this invention encompasses oxidematerials such as alumina, “mixed oxide” compounds thereof such assilica-alumina, and combinations and mixtures thereof. The mixed oxidecompounds such as silica-alumina single chemical phases with more thanone metal combined with oxygen to form a solid oxide compound, and areencompassed by this invention.

In one aspect of this invention, the chemically-treated solid oxidefurther comprises a metal or metal ion selected from zinc, nickel,vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or anycombination thereof. Examples of chemically-treated solid oxides thatfurther comprise a metal or metal ion include, but are not limited to,zinc-impregnated chlorided alumina, zinc-impregnated fluorided alumina,zinc-impregnated chlorided silica-alumina, zinc-impregnated fluoridedsilica-alumina, zinc-impregnated sulfated alumina, or any combinationthereof.

In another aspect, the chemically-treated solid oxide of this inventioncomprises a solid oxide of relatively high porosity, which exhibitsLewis acidic or Brønsted acidic behavior. The solid oxide ischemically-treated with an electron-withdrawing component, typically anelectron-withdrawing anion, to form a chemically-treated solid oxide.While not intending to be bound by the following statement, it isbelieved that treatment of the inorganic oxide with anelectron-withdrawing component augments or enhances the acidity of theoxide. Thus, the chemically-treated solid oxide exhibits Lewis orBrønsted acidity which is typically greater than the Lewis or Brønstedacidity of the untreated solid oxide. One method to quantify the acidityof the chemically-treated and untreated solid oxide materials is bycomparing the polymerization activities of the treated and untreatedoxides under acid catalyzed reactions.

In one aspect, the chemically-treated solid oxide comprises a solidinorganic oxide comprising oxygen and at least one element selected fromGroup 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodictable, or comprising oxygen and at least one element selected from thelanthanide or actinide elements. (See: Hawley's Condensed ChemicalDictionary, 11^(th) Ed., John Wiley & Sons; 1995; Cotton, F. A.;Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced InorganicChemistry, 6^(th) Ed., Wiley-Interscience, 1999.) Usually, the inorganicoxide comprises oxygen and at least one element selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be usedin the chemically-treated solid oxide of the present invention include,but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, CO₃O₄, Cr₂O₃, CuO,Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO,ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixedoxides thereof, and combinations thereof. Examples of mixed oxides thatcan be used in the chemically-treated solid oxide of the presentinvention include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, clays, alumina-titania,alumina-zirconia, aluminum phosphate, heteropolytungstates, and thelike.

In one aspect of this invention, the solid oxide material ischemically-treated by contacting it with at least oneelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material is optionallychemically-treated with a metal ion, then calcining to form ametal-containing or metal-impregnated chemically-treated solid oxide.Alternatively, a solid oxide material and an electron-withdrawing anionsource are contacted and calcined simultaneously. The method by whichthe oxide is contacted with an electron-withdrawing component, typicallya salt or an acid of an electron-withdrawing anion, includes, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. Typically, following any contacting method, thecontacted mixture of oxide compound, electron-withdrawing anion, andoptionally the metal ion is calcined.

The electron-withdrawing component used to treat the oxide is anycomponent that increases the Lewis or Brønsted acidity of the solidoxide upon treatment. In one aspect, the electron-withdrawing componentis an electron-withdrawing anion derived from a salt, an acid, or othercompound such as a volatile organic compound that may serve as a sourceor precursor for that anion. Examples of electron-withdrawing anionsinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, trifluoroacetate, triflate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsmay also be employed in the present invention.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt may beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components may be contacted with the oxide materialsimultaneously or individually, and any order that affords the desiredactivator-support acidity.

Once the solid oxide has been treated and dried, it is subsequentlycalcined. Calcining of the treated solid oxide is generally conducted inan ambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. In another aspect, calcining is conductedat a temperature from about 300° C. to about 800° C. and in anotheraspect, calcining is conducted at a temperature from about 400° C. toabout 700° C. In yet another aspect, calcining is conducted from about 1hour to about 50 hours, and in another aspect calcining is conducted,from about 3 hours to about 20 hours. In still another aspect, when thetreated solid oxide is fluorided silica-alumina, calcining may becarried out from about 1 to about 10 hours at a temperature from about350° C. to about 550° C.

Further, any type of suitable ambient can be used during calcining.Generally, calcining is conducted in an oxidizing atmosphere, such asair. Alternatively, an inert atmosphere, such as nitrogen or argon, or areducing atmosphere such as hydrogen or carbon monoxide, may be used.

In another aspect of the invention, the solid oxide component used toprepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. In another aspect, the solid oxide component has apore volume greater than about 0.5 cc/g, and in yet another aspect,greater than about 1.0 cc/g. In still another aspect, the solid oxidecomponent has a surface area from about 100 to about 1000 m²/g. Inanother aspect, solid oxide component has a surface area from about 200to about 800 m²/g, and in still another aspect, from about 250 to about600 m²/g.

The solid oxide material may be treated with a source of halide ion orsulfate ion, or a combination of anions, and optionally treated with ametal ion, then calcined to provide the activator-support in the form ofa particulate solid. Thus, the treated solid oxide component isgenerally selected from a halided or sulfated solid oxide component, ahalided or a sulfated metal-containing solid oxide component, or acombination thereof. In one aspect of this invention, the treated solidoxide activator-support is selected from treated alumina, treatedsilica-alumina, or mixtures thereof. In another aspect, the treatedalumina is selected from chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided alumina or silica-aluminaor silica-zirconia, bromided silica-alumina, or mixtures thereof, eachoptionally having been treated with a metal ion. In yet another aspect,the treated metal oxide is selected from chlorided alumina, sulfatedalumina, fluorided silica-alumina, or mixtures thereof, each optionallyhaving been treated with a metal ion.

In one aspect of this invention, the treated oxide activator-supportcomprises a fluorided solid oxide in the form of a particulate solid,thus a source of fluoride ion is added to the oxide by treatment with afluoriding agent. In still another aspect, fluoride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent such asalcohol or water, including, but are not limited to, the one to threecarbon alcohols because of their volatility and low surface tension.Examples of fluoriding agents that can be used in this inventioninclude, but are not limited to, hydrofluoric acid (HF), ammoniumfluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆), ammonium hexafluorophosphate (NH₄PF₆), analogs thereof,and combinations thereof. For example, ammonium bifluoride NH₄HF₂ may beused as the fluoriding agent, due to its ease of use and readyavailability.

In another aspect of the present invention, the solid oxide can betreated with a fluoriding agent during the calcining step. Anyfluoriding agent capable of thoroughly contacting the solid oxide duringthe calcining step can be used. For example, in addition to thosefluoriding agents described previously, volatile organic fluoridingagents may be used. Examples of volatile organic fluoriding agentsuseful in this aspect of the invention include, but are not limited to,freons, perfluorohexane, perfluorobenzene, fluoromethane,trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride orfluorine itself can also be used with the solid oxide is fluoridedduring calcining. One convenient method of contacting the solid oxidewith the fluoriding agent is to vaporize a fluoriding agent into a gasstream used to fluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid, thus a source of chloride ion is added to the oxideby treatment with a chloriding agent. The chloride ion may be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Inanother aspect of the present invention, the solid oxide can be treatedwith a chloriding agent during the calcining step. Any chloriding agentcapable of serving as a source of chloride and thoroughly contacting theoxide during the calcining step can be used. For example, volatileorganic choriding agents may be used. Examples of volatile organicchoriding agents useful in this aspect of the invention include, but arenot limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, and combinationsthereof. Gaseous hydrogen chloride or chlorine itself can also be usedwith the solid oxide during calcining. One convenient method ofcontacting the oxide with the chloriding agent is to vaporize achloriding agent into a gas stream used to fluidize the solid oxideduring calcination.

In one aspect, the amount of fluoride or chloride ion present beforecalcining the solid oxide is generally from about 2 to about 50% byweight, where the weight percents are based on the weight of the solidoxide, for example silica-alumina, before calcining. In another aspect,the the amount of fluoride or chloride ion present before calcining thesolid oxide is from about 3 to about 25% by weight, and in anotheraspect, from about 4 to about 20% by weight. If the fluoride or chlorideion are added during calcining, such as when calcined in the presence ofCCl₄, there is typically no fluoride or chloride ion in the solid oxidebefore calcining. Once impregnated with halide, the halided oxide may bedried by any method known in the art including, but not limited to,suction filtration followed by evaporation, drying under vacuum, spraydrying, and the like, although it is also possible to initiate thecalcining step immediately without drying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina can have apore volume greater than about 0.5 cc/g. In one aspect, the pore volumemay be greater than about 0.8 cc/g, and in another aspect, the porevolume may be greater than about 1.0 cc/g. Further, the silica-aluminamay have a surface area greater than about 100 m²/g. In one aspect, thesurface area is greater than about −250 m²/g, and in another aspect, thesurface area may be greater than about 350 m²/g. Generally, thesilica-alumina of this invention has an alumina content from about 5 toabout 95%. In one aspect, the alumina content may be from about 5 toabout 50%, and in another aspect, the alumina content may be from about8% to about 30% alumina by weight.

The sulfated solid oxide comprises sulfate and a solid oxide componentsuch as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is further treated with a metal ion suchthat the calcined sulfated oxide comprises a metal. In one aspect, thesulfated solid oxide comprises sulfate and alumina. In one aspect ofthis invention, the sulfated alumina is formed by a process wherein thealumina is treated with a sulfate source, for example selected from, butnot limited to, sulfuric acid or ammonium sulfate.

In addition to being treated with an electron-withdrawing component suchas halide or sulfate ion, the solid inorganic oxide of this inventionmay optionally be treated with a metal source, including metal salts ormetal-containing compounds. In one aspect of the invention, thesecompounds may be added to or impregnated onto the solid oxide insolution form, and subsequently converted into the supported metal uponcalcining. Accordingly, the solid inorganic oxide can further comprise ametal selected from zinc, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, or a combination thereof. For example, zincmay be used to impregnate the solid oxide because it provides goodcatalyst activity and low cost. The solid oxide may be treated withmetal salts or metal-containing compounds before, after, or at the sametime that the solid oxide is treated with the electron-withdrawinganion.

Further, any method of impregnating the solid oxide material with ametal may be used. The method by which the oxide is contacted with ametal source, typically a salt or metal-containing compound, includes,but is not limited to, gelling, co-gelling, impregnation of one compoundonto another, and the like. Following any contacting method, thecontacted mixture of oxide compound, electron-withdrawing anion, and themetal ion is typically calcined. Alternatively, a solid oxide material,an electron-withdrawing anion source, and the metal salt ormetal-containing compound are contacted and calcined simultaneously.

One aspect of this invention encompasses a process to produce a catalystcomposition comprises contacting(η⁵-cyclopentadienyl)titanium(triphenylstannoxy)dichloride, a chloridedzinc-impregnated alumina, and an organoaluminum compound selected fromtriisobutyl aluminum or triethylaluminum to produce the first catalystcomposition. In one aspect, the amount of zinc used may be from about0.5 millimoles to about 5 millimoles of zinc per gram of alumina. Inanother aspect, the chloriding treatment of the alumina comprisesexposing the alumina to a volatile chlorine-containing compound at atemperature from about 500° C. to about 700° C.

The preparation of the treated solid oxide activators is described inU.S. Pat. Nos. 6,107,230, 6,300,271, 6,316,553, 6,355,594, 6,376,415,6,391,816, and 6,395,666, each of which is incorporated herein byreference, in its entirety.

The Organoaluminum Compound

In one aspect, when the activator of the present invention comprises atreated inorganic oxide it may be used in combination with anorganoaluminum compound. Thus, the present invention comprises a methodto prepare a catalyst comprising contacting the organometal compound anda treated inorganic oxide with at least one organoaluminum compound. Oneaspect of this invention involves the use of some organoaluminumcompound is to precontact the other catalyst components prior tointroducing the catalyst into the polymerization reactor, and thebalance of the organoaluminum compound to be introduced directly intothe polymerization reactor. It is not required that the sameorganoaluminum compound used in the optional precontact step with theother catalyst components is the same as the organoaluminum compoundintroduced directly into the polymerization reactor.

Organoaluminum compounds that can be used along with the treated solidoxide to form the activator for a half-sandwich metallocene include, butare not limited to compounds having the following general formula:Al(X⁵)_(n)(X⁶)_(3-n);wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon atoms;(X⁶) is selected from alkoxide or aryloxide, any one of which havingfrom 1 to about 20 carbon atoms, halide, or hydride; and n is a numberfrom 1 to 3, inclusive.

In one aspect of this invention, (X⁵) is an alkyl having from 2 to about10 carbon atoms. In another aspect, (X⁵) is selected from ethyl, propyl,n-butyl, sec-butyl, isobutyl, hexyl, and the like.

In another aspect, (X⁶) is selected from alkoxide or aryloxide, any oneof which having from 1 to about 10 carbon atoms, halide, or hydride. Inyet another aspect, (X⁶) is independently selected from fluoro orchloro.

In the formula Al(X⁵)_(n)(X⁶)_(3-n) is a number from 1 to 3 inclusive.In one aspect of this invention, n is 3. The value of n is notrestricted to be an integer, therefore this formula includessesquihalide compounds.

Generally, examples of organoaluminum compounds that can be used in thisinvention include, but are not limited to, trialkylaluminum compounds,dialkylaluminium halide compounds, alkylaluminum dihalide compounds,alkylaluminum sesquihalide compounds, and combinations thereof. Specificexamples of organoaluminum compounds that can be used in this inventionin the precontacted mixture with the organometal compound and an olefinor acetylene monomer include, but are not limited to, trimethylaluminum(TMA); triethylaluminum (TEA); tripropylaluminum; diethylaluminumethoxide; tributylaluminum; disobutylaluminum hydride;triisobutylaluminum (TIBAL); and diethylaluminum chloride.

One aspect of this invention involves the optional use of some or all ofthe organoaluminum compound to precontact the other catalyst componentsprior to introducing the catalyst into the polymerization reactor. Thebalance of the organoaluminum compound may be introduced directly intothe polymerization reactor. The amounts of organoaluminum compounddisclosed herein include the total amount of organoaluminum compoundused in an optional precontact step, and any additional organoaluminumcompound added in a different step. In one aspect, triethylaluminum(TEA) and triisobutylaluminum (TIBAL) may be used in this aspect of thisinvention.

The Aluminoxane Activator

The present invention provides catalyst compositions comprising one ormore half-sandwich metallocenes, and an activator component. In oneaspect, the activator of this invention comprises at least onealuminoxane activator. Aluminoxanes are also referred to aspoly(hydrocarbyl aluminum oxides). In this aspect, the half-sandwichmetallocene may be contacted with the aluminoxane in a saturatedhydrocarbon compound solvent, though any solvent which is substantiallyinert to the reactants, intermediates, and products of the activationstep can be used. Thus, in one aspect, the catalyst compositions of thepresent invention comprise the composition that results from reaction ofat least one aluminoxane cocatalyst with at least one half-sandwichmetallocene. The catalyst composition formed in this manner may becollected by methods known to those of skill in the art, including butnot limited to filtration, or the catalyst composition may be introducedinto the polymerization reactor without being isolated.

The aluminoxane compound of this invention may be an oligomeric aluminumcompound, wherein the aluminoxane compound can comprise linearstructures, cyclic, or cage structures, or any mixture thereof. Cyclicaluminoxane compounds having the formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and n is an integer from 3 to about 10 are encompassed by thisinvention. The (AlRO)_(n) moiety shown here also constitutes therepeating unit in a linear aluminoxane. Thus, linear aluminoxanes havingthe formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and n is an integer from 1 to about 50, are also encompassed bythis invention.

Further, aluminoxanes may also have cage structures of the formula R^(t)_(5m+a)R^(b) _(m−a)Al_(4m)O_(3m), wherein m is 3 or 4 and a is=n_(Al(3))−n_(O(2))+n_(O(4)); wherein n_(Al(3)) is the number of threecoordinate aluminum atoms, n_(O(2)) is the number of two coordinateoxygen atoms, n_(O(4)) is the number of 4 coordinate oxygen atoms, R^(t)represents a terminal alkyl group, and R^(b) represents a bridging alkylgroup; wherein R is a linear or branched alkyl having from 1 to 10carbon atoms.

In another aspect of this invention, the aluminoxanes that can be usedas an activator in this invention may be any combination of thealuminoxane compounds and structures presented herein.

Thus, aluminoxanes that may be used as activators in this invention aregenerally represented generally by formulas such as (R—Al—O)_(n),R(R—Al—O)_(n)AlR₂, and the like, wherein the R group is typically alinear or branched C₁-C₆ alkyl such as methyl, ethyl, propyl, butyl,pentyl, or hexyl wherein n typically represents an integer from 1 toabout 50. In one embodiment, the aluminoxane compounds of this inventioninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentyl-aluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.

While organoaluminoxanes with different types of R groups areencompassed by the present invention, methyl aluminoxane (MAO), ethylaluminoxane, or isobutyl aluminoxane are typical activators used in thecatalyst compositions of this invention. These aluminoxanes are preparedfrom trimethylaluminum, triethylaluminum, or triisobutylaluminum,respectively, and are sometimes referred to as poly(methyl aluminumoxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide),respectively. It is also within the scope of the invention to use analuminoxane in combination with a trialkylaluminum, such as disclosed inU.S. Pat. No. 4,794,096, which is incorporated herein by reference, inits entirety.

The present invention contemplates many values of n in the aluminoxaneformulas (R—Al—O)_(n) and R(R—Al—O)_(n)AlR₂, and preferably n is atleast about 3. However, depending upon how the organoaluminoxane isprepared, stored, and used, the value of n may be variable within asingle sample of aluminoxane, and such a combination oforganoaluminoxanes are comprised in the methods and compositions of thepresent invention.

Generally, any amount of the aluminoxane capable of activating thehalf-sandwich metallocene may be utilized in this invention. Inpreparing the catalyst composition of this invention, the molar ratio ofthe aluminum in the alumixoane to the half-sandwich metallocene in thecomposition is usually from about 1:1 to about 100,000:1. In one aspect,the molar ratio of the aluminum in the alumixoane to the half-sandwichmetallocene in the composition is from about 5:1 to about 15,000:1. Inanother apsect, the molar ratio of the aluminum in the alumixoane to thehalf-sandwich metallocene in the composition is usually from about 5:1to about 15,000:1. In yet another aspect, the amount of aluminoxaneadded to a polymerization zone is from about 0.01 mg/L to about 1000mg/L, and in another aspect, from about 0.1 mg/L to about 100 mg/L. Instill another aspect of this invention, the amount of aluminoxane usedmay be from about 1 mg/L to abut 50 mg/L.

Organoaluminoxanes can be prepared by various procedures which are wellknown in the art. Examples of organoaluminoxane preparations aredisclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561, each of which isincorporated herein by reference, in its entirety. One example of how analuminoxane may be prepared is as follows. Water which is dissolved inan inert organic solvent may be reacted with an aluminum alkyl compoundsuch as AlR₃ to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic(R—Al—O)_(n) aluminoxane species, both of which are encompassed by thisinvention. Alternatively, organoaluminoxanes may be prepared by reactingan aluminum alkyl compound such as AlR₃ with a hydrated salt, such ashydrated copper sulfate, in an inert organic solvent.

The aluminoxane activator may be supported or unsupported in the presentinvention. If supported, generally the support comprises an inorganicoxide, such as, silica, an aluminate compound, or combinations thereof.The use of a supported activator may result in a heterogeneous catalystcomposition, and an unsupported activator can result in a homogeneouscatalyst composition, and the present invention encompasses bothheterogeneous and homogeneous catalysts.

The Organoboron Activators

In accordance with this invention, the catalyst composition comprises atleast one half-sandwich metallocene compound and an activator. In oneaspect of this invention, the activator comprises an organoboroncompound. In one aspect, the organoboron compound comprises neutralboron compounds, borate salts, or combinations thereof. For example, theorganoboron compounds of this invention can comprise a fluoroorganoboron compound, a fluoroorgano borate compound, or a combinationthereof. Any fluoroorgano boron or fluoroorgano borate compound known inthe art can be utilized. The term fluoroorgano boron compounds has itsusual meaning to refer to neutral compounds of the form BY₃. The termfluoroorgano borate compound also has its usual meaning to refer to themonoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group. Forconvenience, fluoroorgano boron and fluoroorgano borate compounds aretypically referred to collectively by organoboron compounds, or byeither name as the context requires.

Examples of fluoroorgano borate compounds that can be used ascocatalysts in the present invention include, but are not limited to,fluorinated aryl borates such as, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis-(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and the like, includingmixtures thereof. Examples of fluoroorgano boron compounds that can beused as cocatalysts in the present invention include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)-phenyl]boron, and the like, includingmixtures thereof.

Although not intending to be bound by the following theory, theseexamples of fluoroorgano borate and fluoroorgano boron compounds, andrelated compounds, are thought to form “weakly-coordinating” anions whencombined with organometal compounds, as disclosed in U.S. Pat. No.5,919,983, which is incorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be utilized in thisinvention. In one aspect, the molar ratio of the organoboron compound tothe metallocene compound in the composition is from about 0.1:1 to about10:1. In another aspect, the amount of the fluoroorgano boron orfluoroorgano borate compound used as a cocatalyst or activator for themetallocene is in a range of from about 0.5 mole to about 10 moles ofboron compound per mole of metallocene compound. In one aspect, theamount of fluoroorgano boron or fluoroorgano borate compound used as acocatalyst or activator for the metallocene is in a range of from about0.8 mole to about 5 moles of boron compound per mole of metallocenecompound.

Like the aluminoxane activator, the fluoroorgano boron or fluoroorganoborate activators may be supported or unsupported in the presentinvention. If supported, generally the support comprises an inorganicoxide, such as, silica, an aluminate compound, or combinations thereof.The use of a supported activator may result in a heterogeneous catalystcomposition, and an unsupported activator can result in a homogeneouscatalyst composition, and the present invention encompasses bothheterogeneous and homogeneous catalysts.

The Ionizing Ionic Compound

In accordance with this invention, the catalyst composition comprises atleast one half-sandwich metallocene compound and an activator. In oneaspect of this invention, the activator comprises at least one ionizingionic compound. Examples of ionizing ionic compound are disclosed inU.S. Pat. Nos. 5,576,259 and 5,807,938, each of which is incorporatedherein by reference, in its entirety.

An ionizing ionic compound is an ionic compound which can function toactivate or enhance the activity of the catalyst composition. While notbound by theory, it is believed that the ionizing ionic compound may becapable of reacting with the metallocene compound and converting themetallocene into a cationic metallocene compound. Again, while notintending to be bound by theory, it is believed that the ionizing ioniccompound may function as an ionizing compound by completely or partiallyextracting an anionic ligand, possibly a non-η⁵-alkadienyl ligand suchas (X³) or (X⁴), from the metallocene. However, the ionizing ioniccompound is an activator regardless of whether it is ionizes themetallocene, abstracts an (X³) or (X⁴) ligand in a fashion as to form anion pair, weakens the metal-(X³) or metal-(X⁴) bond in the metallocene,simply coordinates to any ligand ligand, or any other mechanisms bywhich activation may occur. Further, it is not necessary that theionizing ionic compound activate the half-sandwich metallocene only. Theactivation function of the ionizing ionic compound is evident in theenhanced activity of catalyst composition as a whole, as compared to acatalyst composition containing catalyst composition that does notcomprise any ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)-ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)-borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)-ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethyl-phenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate,lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate,lithium tetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl)borate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate,tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(m-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)aluminate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)aluminate, N,N-dimethylaniliniumtetrakis(p-tolyl)-aluminate, N,N-dimethylaniliniumtetrakis(m-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate, triphenylcarbeniumtetrakis(p-tolyl)aluminate, triphenylcarbeniumtetrakis(m-tolyl)aluminate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis-(pentafluorophenyl)aluminate, tropyliumtetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate,tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropyliumtetrakis(3,5-dimethylphenyl)aluminate, tropyliumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis-(phenyl)aluminate, lithium tetrakis(p-tolyl)aluminate, lithiumtetrakis(m-tolyl)aluminate, lithiumtetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate,potassium tetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,However, the ionizing ionic compound is not limited thereto in thepresent invention.

The Olefin Monomer

Unsaturated reactants that are useful in the polymerization processeswith catalyst compositions and processes of this invention includeolefin compounds having from about 2 to about 30 carbon atoms permolecule and having at least one olefinic double bond. This inventionencompasses homopolymerization processes using a single olefin such asethylene or propylene, as well as copolymerization reactions with atleast one different olefinic compound. In one aspect of acopolymerization reaction of ethylene, copolymers of ethylene comprise amajor amount of ethylene (>50 mole percent) and a minor amount ofcomonomer <50 mole percent), though this is not a requirement. Thecomonomers that can be copolymerized with ethylene should have fromthree to about 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins may be employed in this invention. For example, typicalunsaturated compounds that may be polymerized with the catalysts of thisinvention include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, the five normal decenes, and mixturesof any two or more thereof. Cyclic and bicyclic olefins, including butnot limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene,and the like, may also be polymerized as described above.

In one aspect, when a copolymer is desired, the monomer ethylene may becopolymerized with a comonomer. In another aspect, examples of thecomonomer include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normaloctenes, the four normal nonenes, or the five normal decenes. In anotheraspect, the comonomer may be selected from 1-butene, 1-pentene,1-hexene, 1-octene, 1-decene, or styrene.

In one aspect, the amount of comonomer introduced into a reactor zone toproduce the copolymer is generally from about 0.01 to about 10 weightpercent comonomer based on the total weight of the monomer andcomonomer. In another aspect, the amount of comonomer introduced into areactor zone is from about 0.01 to about 5 weight percent comonomer, andin still another aspect, from about 0.1 to about 4 weight percentcomonomer based on the total weight of the monomer and comonomer.Alternatively, an amount sufficient to give the above describedconcentrations by weight, in the copolymer produced can be used.

While not intending to be bound by this theory, in the event thatbranched, substituted, or functionalized olefins are used as reactants,it is believed that steric hindrance may impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. In one aspect, at least one reactant for the catalystcompositions of this invention is ethylene, so the polymerizations areeither homopolymerizations or copolymerizations with a differentacyclic, cyclic, terminal, internal, linear, branched, substituted, orunsubstituted olefin. In addition, the catalyst compositions of thisinvention may be used in polymerization of diolefin compounds, includingbut are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and1,5-hexadiene.

Preparation of the Catalyst Composition

In accordance with this invention, the catalyst compositions wereprepared by a process comprising contacting various combinations of ahalf-sandwich metallocene with an activator for an effective period oftime, prior to using this catalyst composition in the polymerizationprocess. The contact process of preparing the catalyst of this inventionmay be carried out in an inert atmosphere and under substantiallyanhydrous conditions. In one aspect, the atmosphere is substantiallyoxygen-free and substantially free of water as the reaction begins, toprevent deactivation of the catalyst. This contacting procedure canoccur in a variety of ways including, but not limited to, blending ormixing. Further, each of the catalyst composition components can be fedinto the reactor separately, or various combinations of these compoundscan be contacted together prior to being further contacted withadditional catalyst components, or all three compounds can be contactedtogether before being introduced into the reactor.

In one aspect of this invention, the catalyst composition is prepared bycontacting the metallocene compound and the chemically-treated solidoxide component to form a first mixture, and then contacting this firstmixture with an organoaluminum compound to form a second mixturecomprising the catalyst composition. In the first mixture, themetallocene compound and the chemically-treated solid oxide componentmay be contacted from about 1 minute to about 24 hours at a temperaturefrom about 10° C. to about 100° C. In another aspect, the metallocenecompound and the chemically-treated solid oxide component may becontacted from about 1 minute to about 1 hour at a temperature fromabout 15° C. to about 50° C.

In another aspect of this invention, the catalyst composition isprepared by contacting the metallocene compound, the organoaluminumcompound, and the chemically-treated solid oxide component beforeinjection into a polymerization reactor. In this aspect, themetallocene, organoaluminum compound, and the chemically-treated solidoxide are contacted for a period from about 1 minute to about 24 hours.In one aspect, this contact step occurs from about 1 minute to about 1hour, and at a temperature from about 10° C. to about 200° C. In anotheraspect, this contact step occurs at a temperature from about 20° C. toabout 80° C.

One another aspect of this invention is contacting a half-sandwichmetallocene such as (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ with an organoaluminumcompound such as Al(isobutyl)₃ for about 30 minutes to form a firstmixture, prior to contacting this first mixture with anchemically-treated solid oxide activator-support such as chloridedsilica-alumina to form a second mixture. Once the second mixture of allthe catalyst components is formed, it is optionally allowed to remain incontact from about 1 minute to about 24 hours prior to using this secondmixture in a polymerization process.

Another aspect of this invention is contacting a half-sandwichmetallocene such as (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ with an organoaluminumcompound such as Al(isobutyl)₃ and with an α-olefin monomer such as1-hexene for about 30 minutes to form a first mixture, prior tocontacting this first mixture with an acidic activator-support such aschlorided zinc-alumina to form a second mixture. Once the second mixtureof all the catalyst components is formed, it is optionally allowed toremain in contact from about 1 minute to about 24 hours prior to usingthis second mixture in a polymerization process.

In one aspect, the weight ratio of the organoaluminum compound to thetreated solid oxide component in the catalyst composition may be fromabout 5:1 to about 1:1000. In another aspect, the weight ratio of theorganoaluminum compound to the treated solid oxide component in thecatalyst composition may be from about 3:1 to about 1:100, and inanother aspect, from about 1:1 to about 1:50. These weight ratios arebased on the combined weights of organoaluminum, treated oxide, andmetallocene used to prepare the catalyst composition, regardless of theorder of contacting the catalyst components.

In another aspect, the weight ratio of the treated solid oxide componentto the metallocene compound in the catalyst composition may be fromabout 10,000:1 to about 1:1. In another aspect, the weight ratio of thetreated solid oxide component to the metallocene compound in thecatalyst composition may be from about 1000:1 to about 10:1, and in yetanother aspect, from about 250:1 to about 20:1. These weight ratios arebased on the combined weights of organoaluminum, treated oxide, andmetallocene used to prepare the catalyst composition, regardless of theorder of contacting the catalyst components.

Utility of the Catalyst Composition in Polymerization Processes

Polymerizations using the catalysts of this invention can be carried outin any manner known in the art. Such polymerization processes include,but are not limited to slurry polymerizations, gas phasepolymerizations, solution polymerizations, and the like, includingmulti-reactor combinations thereof. Thus, any polymerization zone knownin the art to produce ethylene-containing polymers can be utilized. Forexample, a stirred reactor can be utilized for a batch process, or thereaction can be carried out continuously in a loop reactor or in acontinuous stirred reactor.

After catalyst activation, a catalyst composition is used tohomopolymerize ethylene, or copolymerize ethylene with a comonomer. Inone aspect, a typical polymerization method is a slurry polymerizationprocess (also known as the particle form process), which is well knownin the art and is disclosed, for example in U.S. Pat. No. 3,248,179,which is incorporated by reference herein, in its entirety. Otherpolymerization methods of the present invention for slurry processes arethose employing a loop reactor of the type disclosed in U.S. Pat. No.3,248,179, and those utilized in a plurality of stirred reactors eitherin series, parallel, or combinations thereof, wherein the reactionconditions are different in the different reactors, which is alsoincorporated by reference herein, in its entirety.

In one aspect, polymerization temperature for this invention may rangefrom about 60° C. to about 280° C., and in another aspect,polymerization reaction temperature may range from about 70° C. to about110° C.

The polymerization reaction typically occurs in an inert atmosphere,that is, in atmosphere substantial free of oxygen and undersubstantially anhydrous conditions, thus, in the absence of water as thereaction begins. Therefore a dry, inert atmosphere, for example, drynitrogen or dry argon, is typically employed in the polymerizationreactor.

The polymerization reaction pressure can be any pressure that does notadversely affect the polymerization reaction, and it typically conductedat a pressure higher than the pretreatment pressures. In one aspect,polymerization pressures may be from about atmospheric pressure to about1000 psig. In another aspect, polymerization pressures may be from about50 psig to about 800 psig. Further, hydrogen can be used in thepolymerization process of this invention to control polymer molecularweight.

Polymerizations using the catalysts of this invention can be carried outin any manner known in the art. Such processes that can polymerizemonomers into polymers include, but are not limited to slurrypolymerizations, gas phase polymerizations, solution polymerizations,and multi-reactor combinations thereof. Thus, any polymerization zoneknown in the art to produce olefin-containing polymers can be utilized.For example, a stirred reactor can be utilized for a batch process, orthe reaction can be carried out continuously in a loop reactor or in acontinuous stirred reactor. Typically, the polymerizations disclosedherein are carried out using a slurry polymerization process in a loopreaction zone. Suitable diluents used in slurry polymerization are wellknown in the art and include hydrocarbons which are liquid underreaction conditions. The term “diluent” as used in this disclosure doesnot necessarily mean an inert material, as this term is meant to includecompounds and compositions that may contribute to polymerizationprocess. Examples of hydrocarbons that can be used as diluents include,but are not limited to, cyclohexane, isobutane, n-butane, propane,n-pentane, isopentane, neopentane, and n-hexane. Typically, isobutane isused as the diluent in a slurry polymerization. Examples of thistechnology are found in U.S. Pat. Nos. 4,424,341; 4,501,885; 4,613,484;4,737,280; and 5,597,892; each of which is incorporated by referenceherein, in its entirety.

For purposes of the invention, the term polymerization reactor includesany polymerization reactor or polymerization reactor system known in theart that is capable of polymerizing olefin monomers to producehomopolymers or copolymers of the present invention. Such reactors cancomprise slurry reactors, gas-phase reactors, solution reactors, or anycombination thereof. Gas phase reactors can comprise fluidized bedreactors or tubular reactors. Slurry reactors can comprise verticalloops or horizontal loops. Solution reactors can comprise stirred tankor autoclave reactors.

Polymerization reactors suitable for the present invention can compriseat least one raw material feed system, at least one feed system forcatalyst or catalyst components, at least one reactor system, at leastone polymer recovery system or any suitable combination thereof.Suitable reactors for the present invention can further comprise anyone, or combination of, a catalyst storage system, an extrusion system,a cooling system, a diluent recycling system, or a control system. Suchreactors can comprise continuous take-off and direct recycling ofcatalyst, diluent, and polymer. Generally, continuous processes cancomprise the continuous introduction of a monomer, a catalyst, and adiluent into a polymerization reactor and the continuous removal fromthis reactor of a suspension comprising polymer particles and thediluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor per system or multiple reactor systems comprising two ormore types of reactors operated in parallel or in series. Multiplereactor systems can comprise reactors connected together to performpolymerization, or reactors that are not connected. The polymer can bepolymerized in one reactor under one set of conditions, and then thepolymer can be transferred to a second reactor for polymerization undera different set of conditions.

In one aspect of the invention, the polymerization reactor system cancomprise at least one loop slurry reactor. Such reactors are known inthe art and can comprise vertical or horizontal loops. Such loops cancomprise a single loop or a series of loops. Multiple loop reactors cancomprise both vertical and horizontal loops. The slurry polymerizationcan be performed in an organic solvent that can disperse the catalystand polymer. Examples of suitable solvents include butane, hexane,cyclohexane, octane, and isobutane. Monomer, solvent, catalyst and anycomonomer are continuously fed to a loop reactor where polymerizationoccurs. Polymerization can occur at low temperatures and pressures.Reactor effluent can be flashed to remove the solid resin.

In yet another aspect of this invention, the polymerization reactor cancomprise at least one gas phase reactor. Such systems can employ acontinuous recycle stream containing one or more monomers continuouslycycled through the fluidized bed in the presence of the catalyst underpolymerization conditions. The recycle stream can be withdrawn from thefluidized bed and recycled back into the reactor. Simultaneously,polymer product can be withdrawn from the reactor and new or freshmonomer can be added to replace the polymerized monomer. Such gas phasereactors can comprise a process for multi-step gas-phase polymerizationof olefins, in which olefins are polymerized in the gaseous phase in atleast two independent gas-phase polymerization zones while feeding acatalyst-containing polymer formed in a first polymerization zone to asecond polymerization zone.

In still another aspect of the invention, the polymerization reactor cancomprise a tubular reactor. Tubular reactors can make polymers by freeradical initiation, or by employing the catalysts typically used forcoordination polymerization. Tubular reactors can have several zoneswhere fresh monomer, initiators, or catalysts are added. Monomer can beentrained in an inert gaseous stream and introduced at one zone of thereactor. Initiators, catalysts, and/or catalyst components can beentrained in a gaseous stream and introduced at another zone of thereactor. The gas streams are intermixed for polymerization. Heat andpressure can be employed appropriately to obtain optimal polymerizationreaction conditions.

In another aspect of the invention, the polymerization reactor cancomprise a solution polymerization reactor. During solutionpolymerization, the monomer is contacted with the catalyst compositionby suitable stirring or other means. A carrier comprising an inertorganic diluent or excess monomer can be employed. If desired, themonomer can be brought in the vapor phase into contact with thecatalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed during polymerization toobtain better temperature control and to maintain uniform polymerizationmixtures throughout the polymerization zone. Adequate means are utilizedfor dissipating the exothermic heat of polymerization. Thepolymerization can be effected in a batch manner, or in a continuousmanner. The reactor can comprise a series of at least one separator thatemploys high pressure and low pressure to separate the desired polymer.

In a further aspect of the invention, the polymerization reactor systemcan comprise the combination of two or more reactors. Production ofpolymers in multiple reactors can include several stages in at least twoseparate polymerization reactors interconnected by a transfer devicemaking it possible to transfer the polymers resulting from the firstpolymerization reactor into the second reactor. The desiredpolymerization conditions in one of the reactors can be different fromthe operating conditions of the other reactors. Alternatively,polymerization in multiple reactors can include the manual transfer ofpolymer from one reactor to subsequent reactors for continuedpolymerization. Such reactors can include any combination including, butnot limited to, multiple loop reactors, multiple gas reactors, acombination of loop and gas reactors, a combination of autoclavereactors or solution reactors with gas or loop reactors, multiplesolution reactors, or multiple autoclave reactors.

After the polymers are produced, they can be formed into variousarticles, including but not limited to, household containers, utensils,film products, drums, fuel tanks, pipes, geomembranes, and liners.Various processes can form these articles. Usually, additives andmodifiers are added to the polymer in order to provide desired effects.By using the invention described herein, articles can likely be producedat a lower cost, while maintaining most or all of the unique propertiesof polymers produced with metallocene catalysts.

Definitions

In order to more clearly define the terms used herein, the followingdefinitions are provided. To the extent that any definition or usageprovided by any document incorporated herein by reference conflicts withthe definition or usage provided herein, the definition or usageprovided herein controls.

The term polymer is used herein to mean homopolymers comprising ethyleneand/or copolymers of ethylene and another olefinic comonomer. Polymer isalso used herein to mean homopolymers and copolymers of acetylenes.

The term inert atmosphere is used herein to refer to any type of ambientatmosphere that is substantially unreactive toward the particularreaction, process, or material around which the atmosphere surrounds orblankets. Thus, this term is typically used herein to refer to the useof a substantially oxygen-free and moisture-free blanketing gas,including but not limited to dry argon, dry nitrogen, dry helium, ormixtures thereof, when any precursor, component, intermediate, orproduct of a reaction or process is sensitive to particular gases ormoisture. Additionally, inert atmosphere is also used herein to refer tothe use of dry air as a blanketing atmosphere when the precursors,components, intermediates, or products of the reaction or process areonly moisture-sensitive and not oxygen-sensitive. However, inertatmosphere, as used herein, would typically exclude CO₂ or CO becausethese gases may be reactive toward the particular reaction, process, ormaterial around which they would surround or blanket, despite theiroccasional use as inert blanketing gases in other processes.

The term half-sandwich metallocene is used herein to refer tometallocene and metallocene-like compounds containing only oneη⁵-alkadienyl ligand, typically one η⁵-cycloalkadienyl ligand, and inone aspect, one η⁵-cyclopentadienyl ligand, or its analogs orderivatives. Thus, the metallocenes of this invention typically comprisea cyclopentadienyl, indenyl, fluorenyl, or boratabenzene ligand, orsubstituted derivatives thereof. Possible substituents on these ligandsinclude hydrogen, therefore the description “substituted derivativesthereof” in this invention comprises partially saturated ligands such astetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partiallysaturated indenyl, partially saturated fluorenyl, substituted partiallysaturated indenyl, substituted partially saturated fluorenyl, and thelike.

The terms catalyst composition, catalyst mixture, and the like are usedherein to refer to the mixture of catalyst components disclosed herein,regardless of the actual product of the reaction of the components, thenature of the active catalytic site, or the fate of any one componentsuch as organometal compound and activator. Therefore, the termscatalyst composition, catalyst mixture, and the like include bothheterogeneous compositions and homogenous compositions.

The term hydrocarbyl is used to specify a hydrocarbon radical group thatincludes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl,cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl,and the like, and includes all substituted, unsubstituted, branched,linear, heteroatom substituted derivatives thereof.

The terms activator, cocatalyst, and related terms are genericdescriptors used to refer to the compounds, compositions, or mixturesthat are contacted with the half-sandwich metallocenes to form thecatalyst compositions of this invention, regardless of any particularreaction or mechanism by which such compounds, compositions, or mixturesfunction. Activators include, but are not limited to: compounds such asan aluminoxane, an organoboron compound, an ionizing ionic compound, aclay material, a chemically-treated solid oxide combined with anorganoaluminum compound, or any combination thereof. In another aspect,the term activator is used to refer to compositions or mixtures,examples of which include, but are not limited to, mixtures ofchemically-treated solid oxides and organoaluminum compounds, andmixtures of clays or other layered materials and organoaluminumcompounds.

The term chemically-treated solid oxide is used interchangeably withterms such as solid acidic activator-support, acidic activator-support,or simply activator-support, and the like to indicate achemically-treated, solid, inorganic oxide of relatively high porosity,which exhibits enhanced Lewis acidic or Brønsted acidic behavior,arising through treatment of the solid oxide with anelectron-withdrawing component, typically an electron-withdrawing anionor an electron-withdrawing anion source compound. These terms are notused to imply this component is inert, and it should not be construed asan inert component of the catalyst composition. Rather, thechemically-treated solid oxides in combination with the organoaluminumcompounds comprise activators of the half-sandwich metallocenes andcomprise an insoluble component of the catalyst composition of thisinvention to produce polymers, and at which the active catalytic sitesare situated, and are not intended to be limiting.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed above and throughout the text areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the inventors are not entitled to antedate such disclosure byvirtue of prior invention.

For any particular compound disclosed herein, any general structurepresented also encompasses all conformational isomers, regioisomers, andstereoisomers that may arise from a particular set of substitutents. Thegeneral structure also encompasses all enantiomers, diastereomers, andother optical isomers whether in enantiomeric or racemic forms, as wellas mixtures of stereoisomers, as the context requires.

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort may be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

In the following examples, unless otherwise specified, the syntheses andpreparations described therein were carried out under an inertatmosphere such as nitrogen and/or argon. Solvents were purchased fromcommercial sources and were typically dried over activated alumina priorto use, or distilled from potassium metal prior to use. Unless otherwisespecified, reagents were obtained from commercial sources.

EXAMPLE 1

Testing Methods

A “Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument,”acquired from the Quantachrome Corporation, Syosset, N.Y., was used todetermined surface areas and pore volumes of the treated oxideactivator-supports of this invention. The melt Index (MI) of the polymerproduct was determined using a 2.16 kg load and High Load Melt Index(HLMI) was determined with a 21.6 kg load at 190° C.

EXAMPLE 2

Preparation of (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂

Triphenyltin hydroxide, 1.76 g (4.8 mmoles), was dissolved in 25 mL ofdry THF. To this solutions was added dropwise a solution of 25 mL of THFand 3.0 mL (4.8 mmoles) of n-butyl lithium in hexanes. This reactionmixture was stirred for 2 hours. The resulting, slightly cloudy mixturewas added dropwise to a solution of 1.05 g (4.8 mmoles) of(η⁵-C₅H₅)TiCl₃ in 25 mL of THF over 1 hour. After stirring overnight,the slurry was filtered through Celite (diatomaceous earth), and thefiltrate was then concentrated until a yellow solid began to form (20-25mL). After cooling overnight in a freezer (at about −15° C.), themixture was cooled in dry ice for 3 hours and then filtered. Theresulting yellow powder was washed with heptane and dried to give 0.62 gof product.

EXAMPLE 3

General Sources and Properties of the Solid Oxide Materials Used toPrepare the Treated Solid Oxides

Alumina was obtained as Ketjen™ grade B from Akzo Nobel, having a porevolume of about 1.78 cc/g and a surface area of about 340 m²/g orKetjen™ L 95-98% alumina and 2-5% silica having a pore volume of 2.00cc/g and surface area of 380 m²/g. Silica was obtained as Davison grade952 from W.R. Grace, having a pore volume of about 1.6 cc/g and asurface area of about 300 m²/g. Silica-alumina was obtained as MS13-110from W.R. Grace having 13% by weight alumina and 87% by weight silicaand having a pore volume of about 1.2 cc/g and a surface area of about350 m²/g.

EXAMPLE 4

Preparation of Zinc-Impregnated Chlorided Alumina

Ketjen™ grade B alumina, 544.85 g, was saturated to just past incipientwetness with an aqueous solution of 109 g of zinc chloride in 900 g ofwater and shaken to ensure uniform wetness. The solid was then dried ina vacuum oven at 120° C. and passed through a 80 mesh screen. A portionof the solid was then calcined in air for three hours at 600° C. using a10 inch bed in a 45 mm diameter tube and 0.2 to 0.4 SCFH of nitrogen.After calcining, the furnace temperature was maintained at 600° C., andthe gas stream was changed from air to dry nitrogen. Then, 15 mL ofcarbon tetrachloride were injected into the nitrogen stream andevaporated upstream from the alumina bed. The carbon tetrachloride vaporwas carried up through the bed and reacted with the alumina in order tochloride the surface to produce a chlorided alumina. The chloridedalumina was white in color.

EXAMPLE 5

Preparation of Zinc-Impregnated Fluorided Silica-Alumina

Silica-alumina, sold as MS13-110 by W.R. Grace Company, 114.68 g, havinga surface area of 400 m²/g and a pore volume of 1.2 cc/g, wasimpregnated to just beyond incipient wetness with a solution containing17.6 g of Zn(NO₃)₂.6H₂O and 11.5 g of ammonium bifluoride dissolved in125 mL of water. This mixture was then placed in a vacuum oven and driedovernight at 120° C. under half an atmosphere of vacuum. The final stepin producing this activated-support was to calcine 10 grams of thematerial in dry fluidizing air at 500° C. for three hours, after whichthe zinc-impregnated, treated solid oxide was stored under nitrogenuntil used.

EXAMPLE 6

Preparation of Fluorided Silica-Alumina

Silica-alumina, MS13-110 from W.R. Grace Company, 700 g, was impregnatedto just beyond incipient wetness with a solution containing 70 g ofammonium bifluoride dissolved in 1250 mL of water. This mixture was thenplaced in a vacuum oven and dried overnight at 120° C. under half anatmosphere of vacuum. The final step in producing activated-support wasto calcine the material in dry fluidizing air at 454° C. for 6 hours,after which the treated solid oxide was stored under nitrogen untilused.

EXAMPLE 7

Preparation of Sulfated Alumina

Ketjen™ L alumina, 652 g, was impregnated to just beyond incipientwetness with a solution containing 137 g of (NH₄)₂SO₄ dissolved in 1300mL of water. This mixture was then placed in a vacuum oven and driedovernight at 110° C. under half an atmosphere of vacuum and thencalcined in a muffle furnace at 300° C. for 3 hours, then at 450° C. for3 hours, after which the activated support was screened through an 80mesh screen. The support was then activated in air at 550° C. for 6hours, after which the treated solid oxide was stored under nitrogenuntil used.

EXAMPLE 8

General Description of the Polymerization Runs

Polymerizations were carried out in a 1 gallon Autoclave Engineersstirrer reactor, fitted with an oil-less packing with a flat stirrerrunning at 700 rpm. The reactor temperature was regulated by controllingthe temperature of the water in the steel jacket using steam and waterheat exchangers, with electronic instrumentation to control flows.Catalysts were added while the autoclave temperature was below 40° C.under a purge of isobutane. The autoclave was then sealed and 2 L ofisobutane were added and stirring started at 700 rpm. Reactor heatingwas then initiated and as the reactor temperature approached 60° C.,ethylene addition was initiated. The hexene was flushed in with theethylene from an in-line vessel on top of the reactor. The set pointtemperature and pressure were then rapidly attained. The reactor washeld under these conditions for 60 minutes by feeding ethylene ondemand. The polymerization was then terminated by venting the volatilesto the flare system. This process left the polyethylene as a wet solidin the reactor, which was collected, and the solid air dried to yieldgranular polyethylene. Examples 8a-8c of Table 1 illustratepolymerization runs using the catalysts of this invention.

EXAMPLE 9

Comparative Example Using Non-Stannoxy Metallocene Catalyst

In this example, the non-stannoxy half-sandwich metallocene CpTiCl₃ wasused as a control to compare with the results obtained using thestannoxy-substituted half-sandwich metallocenes of the presentinvention. The compound CpTiCl₃, 7 mg, was mixed with 250 mg of thezinc-impregnated chlorided alumina solid oxide activator (Example 4) ina Diels-Alder tube. Toluene, 4 mL, was added and the mixture was stirredby hand for 5 minutes. This slurry was added to the reactor below 40° C.followed by about half of the isobutene (about 1 L). The reactor heatingwas started and the remaining isobutane (about 1 L) was used to flushthe triisobutylaluminum solution (0.5 mL, 25 wt % in heptane) and 25 gmof 1-hexene from an in-line vessel into the reactor. As the reactortemperature approached 60° C., ethylene addition was begun and the setpoint of 80° C. was then rapidly attained. The reactor was held at 80°C. for 60 minutes and then the volatiles were vented to the flaresystem. This procedure left the polyethylene as free flowing solid inthe reactor; yield 51.8 gm (7400 gm PE/gm metallocene/hr). Thepolyethylene produced in this Example had a HLMI of 0.002 gm/10 minutes.Examples 9a and 9b of Table 1 illustrate additional comparative examplesusing CpTiCl₃ as a catalyst.

EXAMPLE 10

Polymerization Process Using (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ and aZinc-Impregnated Chlorided Alumina Activator-Support

The half-sandwich metallocene(η⁵-cyclopentadienyl)titanium-(triphenylstannoxy)dichloride, 0.007 g,was mixed with 250 mg of the zinc-impregnated chlorided alumina solidoxide activator (Example 4) in a Diels-Alder tube. Toluene, 4 mL, wasadded and the mixture was stirred by hand for 5 minutes. This slurry wasadded to the reactor below 40° C. followed by about half (about 1 L) ofthe isobutane. The reactor heating was started and the remainingisobutane (about 1 L) was used to flush the triisobutylaluminum solution(0.5 mL, 25 wt % in heptane) and 25 gm of 1-hexene from an in-linevessel into the reactor. As the reactor approached 60° C., ethyleneaddition was begun and the set point of 80° C. was then rapidlyattained. The reactor was held there for 60 minutes and then thevolatiles were vented to the flare system. This procedure left thepolyethylene as free flowing solid in the reactor; yield 178.1 gm(25,443 gm PE/gm metallocene/hr). The polyethylene had a HLMI of 0 μm/10minutes. See Table 1.

EXAMPLE 11

Polymerization Process Using (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ and aZinc-Impregnated Chlorided Alumina Activator-Support in the Presence ofHydrogen

The half-sandwich metallocene(η⁵-cyclopentadienyl)titanium-(triphenylstannoxy)dichloride, 7 mg, wasmixed with 250 mg of the zinc-impregnated chlorided alumina solid oxideactivator (Example 4) in a Diels-Alder tube. Toluene, 4 mL, was addedand the mixture was stirred by hand for 5 minutes. This slurry was addedto the reactor below 40° C. followed by about half of the isobutene(about 1 L). The reactor heating was started and the remaining isobutane(about 1 L) was used to flush the triisobutylaluminum solution (0.5 mL,25 wt % in heptane) and 25 gm of 1-hexene from an in-line vessel intothe reactor. In this run, the effect of adding hydrogen to the reactionwas determined by adding a 175 psi pressure drop measured off of a 300mL cylinder of hydrogen to the reactor. As the reactor approached 60°C., ethylene addition was begun and the set point of 80° C. was thenrapidly attained. The reactor was held there for 60 minutes and then thevolatiles were vented to the flare system. This procedure left thepolyethylene as free flowing solid in the reactor; yield 99.6 gm. Thepolyethylene had a MI of 0.366 gm/10 minutes and a HLMI of 19.4 gm/10minutes. See Table 1.

EXAMPLE 12

Polymerization Process Using (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ and a FluoridedSilica-Alumina Activator-Support

The half-sandwich metallocene(η⁵-cyclopentadienyl)titanium-(triphenylstannoxy)dichloride, 7 mg, wasmixed with 250 mg of the fluorided silica-alumina activator-support fromExample 6 in a Diels-Alder tube. Toluene, 4 mL, was added and themixture was stirred by hand for 5 minutes. This slurry was added to thereactor below 40° C. followed by about half of the isobutene (about 1L). The reactor heating was initiated and the remaining isobutene (about1 L) was used to flush the triisobutylaluminum solution (0.5 mL, 25 wt %in heptane) and 25 gm of 1-hexene from an in-line vessel into thereactor. As the reactor temperature approached 60° C., ethylene additionwas begun and the set point of 100° C. was then rapidly attained. Thereactor was held there for 60 minutes and then the volatiles were ventedto the flare system. This procedure left the polyethylene as freeflowing solid in the reactor; yield 16.6 gm. The polyethylene had a HLMIof 0.006 gm/10 minutes. See Table 1.

EXAMPLE 13

Polymerization Process Using (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ and a SulfatedAlumina Activator-Support

The half-sandwich metallocene(η⁵-cyclopentadienyl)titanium-(triphenylstannoxy)dichloride, 7 mg, wasmixed with 250 mg of the sulfated alumina activator-support from Example7 in a Diels-Alder tube. Toluene, 4 mL, was added and the mixture wasstirred by hand for 5 minutes. This slurry was added to the reactorbelow 40° C. followed by about half of the isobutene (about 1 L). Thereactor heating was initiated and the remaining isobutane (about 1 L)was used to flush the triisobutylaluminum solution (0.5 mL, 25 wt % inheptane) and 25 gm of 1-hexene from an in-line vessel into the reactor.As the reactor approached 60° C., ethylene addition was begun and theset point of 80 C was then rapidly attained. The reactor was held therefor 60 minutes and then the volatiles were vented to the flare system.This procedure left the polyethylene as free flowing solid in thereactor; yield 7 gm. The polyethylene had a HLMI of 0.023 gm/10 minutes.See Table 1.

EXAMPLE 14

Polymerization Process Using (η⁵-C₅H₅)Ti[OSn(C₆H₅)₃]Cl₂ and a SulfatedAlumina Activator-Support in the Absence of 1-Hexene

The half-sandwich metallocene(η⁵-cyclopentadienyl)titanium-(triphenylstannoxy)dichloride, 7 mg, wasmixed with 250 mg of the sulfated alumina activator-support from Example7 in a Diels-Alder tube. Toluene, 4 mL, was added and the mixture wasstirred by hand for 5 minutes. This slurry was added to the reactorbelow 40° C. followed by about half of the isobutene (about 1 L). Thereactor heating was initiated and the remaining isobutane (about 1 L)was used to flush the triisobutylaluminum solution (0.5 mL, 25 wt % inheptane) from an in-line vessel into the reactor. In this run, no1-hexene was added to the reaction. As the reactor approached 60° C.,ethylene addition was begun and the set point of 100° C. was thenrapidly attained. The reactor was held there for 60 minutes and then thevolatiles were vented to the flare system. This procedure left thepolyethylene as free flowing solid in the reactor; yield 13 gm. SeeTable 1.

EXAMPLE 15

Polymerization Process Using (η⁵-C₅H₅) Ti[OSn(C₆H₆)₃]Cl₂ andMethylaluminoxane Activator

To a 1 gallon Autoclave Engineers stirrer reactor fitted with anoil-less packing, 10 mL of methylaluminoxane (10% in Toluene) were addedwhile maintaining below 40° C. under a purge of isobutane. Thehalf-sandwich metallocene(η⁵-cyclopentadienyl)titanium(triphenylstannoxy)dichloride, 7 mg, wasthen charged to the autoclave. The autoclave was sealed and 2 L ofisobutane were added and stirring started at 700 rpm. The reactorheating was then initiated. As the reactor approached 60° C., ethyleneaddition was begun. The 25 grams of 1-hexene were flushed in with theethylene from an in-line vessel on top of the reactor. The set point of80° C. and 450 psig was then rapidly attained. The reactor was heldthere for 60 minutes by feeding ethylene on demand. The polymerizationwas terminated by then venting the volatiles to the flare system. Thisprocedure left the polyethylene as a wet solid in the reactor. Thepolyethylene solid was air dried to yield 10.0 grams of product. Asimilar polymerization run (Example 15a) was carried out using MAO incombination with a chlorided zinc alumina, prepared as in Example 4. Theresults of both runs are presented in Table 1. TABLE 1 Co- Reactionmonomer Example Time Temp. Ethylene H₂ Co- Wt. Activator No.Catalyst^(a) (min) (C.) (psig) (Δ psi)^(b) monomer (g) Activator^(c) Wt.(mg) 10 a 60 80 450 0 hexene 25.0 w 250 11 a 60 80 450 175 hexene 25.0 w250 12 a 60 100 550 0 — 0.0 y 250 13 a 60 80 450 0 hexene 25.0 x 250 14a 60 100 550 0 — 0.0 x 250 15 a 60 80 450 0 hexene 25.0 — — 15a a 60 80450 0 hexene 25.0 w 250  8a a 61 80 450 0 hexene 25.0 w 250  8b a 32 80450 0 hexene 25.0 z 250  8c a 60 90 450 0 hexene 20.0 x 250 Controls  9b 60 80 450 0 hexene 25.0 w 250  9a b 60 80 450 0 hexene 25.0 w 250  9bb 60 80 450 132 hexene 25.0 w 250 Produc- Catalyst Activator MI HLMIExample TIBAL Solid PE tivity Activity Activity (g/10 (g/10 No. (mL)^(d)Cat. Wt. (g) (g) (g/g) (g/g/hr) (g/g/hr) min) min) 10 0.5 0.0070 178.125443 25443 712 0.000 0.0000 11 0.5 0.0070 99.6 14229 14229 398 0.36619.4 12 0.5 0.0070 16.6 2370 2370 66 0.000 0.0060 13 0.5 0.0070 7.0 10001000 28 0.000 0.0230 14 0.5 0.0070 13.0 1857 1857 52 15 10 mL 0.007010.0 1429 1429 MAO 15a 10 mL 0.0070 34.5 4929 4929 138 0.000 0.0160 MAO 8a 0.5 0.0070 177.9 25414 24998 700 0.00 0.0  8b 0.0100 0.8 80 150 6 8c 0.5 0.0100 6.4 640 640 26 Controls  9 0.5 0.0070 51.8 7400 7400 2070.00 0.002  9a 0.5 0.0120 88.0 7333 7333 352 0.0  9b 0.5 0.0070 72.610371 10371 290 1.0^(a)Catalyst a is CpCl₂Ti(OSnPh₃); and b is CpTiCl₃.^(b)Pressure drop (psi) in a 300 mL cylinder of H₂ to reactor.^(c)Activator w is chlorided Zn-impregnated Ketjen B alumina (100-200mesh), prepared as in Example 4; x is sulfated Ketjen L alumina,prepared as in Example 7; y is fluorided silica-alumina, prepared as inExample 6; and z is Zn(NO₃)₂ + NH₄HF₂ treated silica-alumina.^(d)Used as a 25 weight % solution in heptane.

1. A compound having the following formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide.
 2. Thecompound of claim 1, wherein the compound has the following generalformula:(η⁵-cycloalkadienyl)M(OSnR₃)X₂; wherein cycloalkadienyl is selected fromcyclopentadienyl, indenyl, fluorenyl, or substituted analogs thereof; Mis selected from Ti, Zr, or Hf; R is independently selected fromsubstituted or non-substituted alkyl, cycloalkyl, aryl, aralkyl,alkoxide, or aryloxide, any one of which having from 1 to about 20carbon atoms; F; Cl; Br; or I; and X is independently selected from F;Cl; Br; I; or a substituted or non-substituted alkyl, cycloalkyl, aryl,aralkyl, alkoxide, or aryloxide, any one of which having from 1 to about20 carbon atoms.
 3. The compound of claim 1, wherein the compound isselected from:(η⁵-cyclopentadienyl)titanium(triphenylstannoxy)dichloride;(η⁵-cyclopentadienyl)zirconium(triphenylstannoxy)dichloride;(η⁵-cyclopentadienyl)titanium(trimethylstannoxy)dichloride;(η⁵-cyclopentadienyl)zirconium(triethylstannoxy)dichloride;(η⁵-cyclopentadienyl)hafnium(triphenylstannoxy)dichloride;(η⁵-cyclopentadienyl)titanium(tri-n-butylstannoxy)dichloride;(η⁵-cyclopentadienyl)titanium(triphenylstannoxy)dibromide;(η⁵-pentamethylcyclopentadienyl)titanium(triphenylstannoxy)dibromide; or(η⁵-cyclopentadienyl)titanium(tributylstannoxy)dibromide.
 4. Acomposition of matter comprising a half-sandwich metallocene compoundwith the following formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide.
 5. A catalystcomposition comprising a half-sandwich metallocene compound with thefollowing formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide.
 6. A catalystcomposition comprising: a) a half-sandwich metallocene compound with thefollowing formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; and b) achemically-treated solid oxide comprising a solid oxide treated with anelectron-withdrawing anion; wherein the solid oxide is selected fromsilica, alumina, silica-alumina, aluminum phosphate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or mixtures thereof; and the electron-withdrawinganion is selected from fluoride, chloride, bromide, phosphate, triflate,bisulfate, sulfate, or any combination thereof.
 7. The catalystcomposition of claim 6, wherein the chemically-treated solid oxidefurther comprises a metal or metal ion.
 8. The catalyst composition ofclaim 6, wherein the chemically-treated solid oxide further comprises ametal or metal ion, and wherein the chemically-treated solid oxide isselected from zinc-impregnated chlorided alumina, zinc-impregnatedfluorided alumina, zinc-impregnated chlorided silica-alumina,zinc-impregnated fluorided silica-alumina, zinc-impregnated sulfatedalumina, or any combination thereof.
 9. The catalyst composition ofclaim 6, wherein the chemically-treated solid oxide further comprises ametal or metal ion selected from zinc, nickel, vanadium, silver, copper,gallium, tin, tungsten, molybdenum, or any combination thereof.
 10. Thecatalyst composition of claim 6, wherein the chemically-treated solidoxide comprises fluorided silica alumina which comprises from about 5%to about 95% by weight alumina and from about 2% to about 50% by weightfluoride ion, based on the weight of the fluorided silica-alumina afterdrying but before calcining.
 11. The catalyst composition of claim 6,wherein the chemically-treated solid oxide is selected from fluoridedalumina, chlorided alumina, bromided alumina, fluorided silica-alumina,chlorided silica-alumina, sulfated alumina, sulfated silica-alumina, ora combination thereof.
 12. A catalyst composition comprising: a) ahalf-sandwich metallocene compound with the following formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; and b) anorganoaluminum compound with the following formula:Al(X⁵)_(n)(X⁶)_(3-n); wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is selected from alkoxide or aryloxide, anyone of which having from 1 to about 20 carbon atoms, halide, or hydride;and n is a number from 1 to 3, inclusive.
 13. A catalyst compositioncomprising: a) a half-sandwich metallocene compound with the followingformula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; and b) anactivator selected from an aluminoxane, an organoboron compound, anionizing ionic compound, a clay material, a chemically-treated solidoxide combined with an organoaluminum compound, or any combinationthereof.
 14. The catalyst composition of claim 13, wherein the activatorcomprises an aluminoxane comprising: a cyclic aluminoxane having theformula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and n is an integer from 3 to about 10; a linear aluminoxanehaving the formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and n is an integer from 1 to about 50; a cage aluminoxane havingthe formula R^(t) _(5m+a)R^(b) _(m−a)Al_(4m)O_(3m), wherein m is 3 or 4and a is =n_(al(3))−n_(O(2))+n_(O(4)); wherein n_(Al(3)) is the numberof three coordinate aluminum atoms, n_(O(2)) is the number of twocoordinate oxygen atoms, n_(O(4)) is the number of 4 coordinate oxygenatoms, R^(t) represents a terminal alkyl group, and R^(b) represents abridging alkyl group; wherein R is a linear or branched alkyl havingfrom 1 to 10 carbon atoms; or any combination thereof.
 15. The catalystcomposition of claim 14, wherein the molar ratio of the aluminum in thealumixoane to the half-sandwich metallocene in the composition is fromabout 1:1 to about 100,000:1.
 16. The catalyst composition of claim 13,wherein the activator comprises an aluminoxane selected frommethylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butyl-aluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane,neopentylaluminoxane, or any combination thereof.
 17. The catalystcomposition of claim 13, wherein the activator comprises an organoboroncompound selected from tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, or a combination thereof. 18.The catalyst composition of claim 17, wherein the molar ratio of theorganoboron compound to the half-sandwich metallocene in the compositionis from about 0.5:1 to about 10:1.
 19. The catalyst composition of claim13, wherein the activator comprises an ionizing ionic compound selectedfrom tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammoniumtetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis-(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate,lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate,lithium tetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetrakis(phenyl)borate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetrakis(phenyl)borate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate,tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(m-tolyl)aluminate, tri(n-butyl)ammoniumtetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)aluminate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)-aluminate, N,N-dimethylaniliniumtetrakis(p-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(m-tolyl)aluminate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)aluminate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)aluminate, triphenylcarbeniumtetrakis(p-tolyl)aluminate, triphenylcarbeniumtetrakis(m-tolyl)aluminate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)aluminate, triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate, tropyliumtetrakis(p-tolyl)aluminate, tropylium tetrakis(m-tolyl)aluminate,tropylium tetrakis(2,4-dimethylphenyl)aluminate, tropyliumtetrakis(3,5-dimethylphenyl)aluminate, tropyliumtetrakis(pentafluorophenyl)aluminate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetrakis(phenyl)aluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetrakis(phenyl)aluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetrakis(phenyl)aluminate, potassium tetrakis(p-tolyl)aluminate,potassium tetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,or any combination thereof.
 20. A catalyst composition comprising: a) ahalf-sandwich metallocene compound with the following formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; b) achemically-treated solid oxide comprising a solid oxide treated with anelectron-withdrawing anion, wherein the solid oxide is selected fromsilica, alumina, silica-alumina, aluminum phosphate,heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or mixtures thereof; and the electron-withdrawinganion is selected from fluoride, chloride, bromide, phosphate, triflate,bisulfate, sulfate, or combinations thereof; and c) an organoaluminumcompound with the following formula:Al(X⁵)_(n)(X⁶)_(3-n); wherein (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is selected from alkoxide or aryloxide, anyone of which having from 1 to about 20 carbon atoms, halide, or hydride;and n is a number from 1 to 3, inclusive.
 21. The catalyst compositionof claim 20, wherein the weight ratio of the organoalumium compound tochemically-treated solid oxide is from about 5:1 to about 1:1000. 22.The catalyst composition of claim 20, wherein the weight ratio of thechemically-treated solid oxide to the half-sandwich metallocene compoundis from about 10,000:1 to about 1:1.
 23. The catalyst composition ofclaim 20, wherein: the solid oxide is selected from silica, alumina,silica-alumina, or mixtures thereof; the electron-withdrawing anion isselected from fluoride, chloride, bromide, phosphate, triflate,bisulfate, sulfate, or any combination thereof; and the organoalumiumcompound is selected from trimethylaluminum (TMA) triethylaluminum(TEA), tripropylaluminum, diethylaluminum ethoxide, tributylaluminum,disobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminumchloride, or any combination thereof.
 24. The catalyst composition ofclaim 20, wherein the half-sandwich metallocene comprises(η⁵-C₅H₅)Ti(OSnPh₃)Cl₂, the chemically-treated solid oxide compriseschlorided zinc-alumina, and the organoaluminum compound comprisestriisobutylaluminum (TIBAL).
 25. A process to produce a catalystcomposition comprising contacting a half-sandwich metallocene compoundand an activator, wherein: a) the half-sandwich metallocene compound hasthe following formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide; and b) theactivator is selected from an aluminoxane, an organoboron compound, anionizing ionic compound, a clay material, a chemically-treated solidoxide combined with an organoaluminum compound, or any combinationthereof.
 26. A process for polymerizing olefins comprising contacting acatalyst composition with at least one type of olefin monomer, whereinthe catalyst composition comprises a half-sandwich metallocene compoundwith the following formula:(X¹)(X²)(X³)(X⁴)M¹; wherein M¹ is selected from titanium, zirconium, orhafnium; (X¹) is selected from cyclopentadienyl, indenyl, fluorenyl,substituted cyclopentadienyl, substituted indenyl, or substitutedfluorenyl; each substituent on the substituted cyclopentadienyl,substituted indenyl, or substituted fluorenyl (X¹) is independentlyselected from an aliphatic group, an aromatic group, a cyclic group, acombination of aliphatic and cyclic groups, an oxygen group, a sulfurgroup, a nitrogen group, a phosphorus group, an arsenic group, a carbongroup, a silicon group, a germanium group, a tin group, a lead group, aboron group, an aluminum group, an inorganic group, an organometallicgroup, or a substituted derivative thereof, any one of which having from1 to about 20 carbon atoms; a halide; or hydrogen; (X²) is selected froma stannoxy group with the following formula:—OSnR₃; wherein R is independently selected from alkyl, cycloalkyl,aryl, aralkyl, substituted alkyl, substituted aryl, or substitutedaralkyl, any one of which having from 1 to about 20 carbon atoms; OR′wherein R′ is selected from alkyl, aryl, aralkyl, substituted alkyl,substituted aryl, or substituted aralkyl, any one of which having from 1to about 20 carbon atoms; F; Cl; Br; or I; and (X³) and (X⁴) areindependently selected from an aliphatic group, an aromatic group, acyclic group, a combination of aliphatic and cyclic groups, an oxygengroup, a sulfur group, a nitrogen group, a phosphorus group, an arsenicgroup, a carbon group, a silicon group, a germanium group, a tin group,a lead group, a boron group, an aluminum group, an inorganic group, anorganometallic group, or a substituted derivative thereof, any one ofwhich having from 1 to about 20 carbon atoms; or a halide.